(thio) phosphoric acid and (thio) phosphonic acid esters and amides

ABSTRACT

Thiochromanone oxime-phosphoric and -phosphonic acid derivatives of the formula   IN WHICH R1 is O-alkyl, NH-alkyl or N-dialkyl; R2 is alkyl, Oalkyl or phenyl; R3 and R4 are each hydrogen or alkyl; R5, R6, R7 and R8 are each hydrogen, alkyl, halogen, alkoxy or alkylthio, and X is oxygen or sulfur, are useful as insecticides, acaricides and nematicides.

United States Patent [1 1 Hiirlein et al.

[ Aug. 19, 1975 Assignee: Hoechst Aktiengesellschaft,

Frankfurt am Main, Germany [22] Filed: Mar. 19, 1973 [21] Appl. No: 342,491

[30] Foreign Application Priority Data U Mar. 24, 1972 Germany 2214297 [52] US. Cl. 260/327 TH; 424/202 [51] Int. Cl C07d 65/08 [58] Field of Search 260/327 TH {56] References Cited FOREIGN PATENTS OR APPLICATIONS 1,164.596 9/l969 United Kingdom 260/327 Primary Examiner-Henry R. Jiles Assistant Exizminjer c. M. S. Jaisle AlturneyAgenr, or Firm-Curtis, Morris & Safford v ABSTRACT Thiochromanone oxime-phosphoric and -phosphonic acid derivatives of the formula in which R is O-alkyl, NH-alkyl or N-dialkyl; R. is alkyl, O-alkyl or phenyl; R and R are each hydrogen or alkyl; R R R and R are each hydrogen, alkyl, halogen, alkoxy or alkylthio, and X is oxygen or sulfur, are useful as insecticides, acaricides and nematicides.

16 Claims, N0 Drawings (THIO) PHOSPHORIC ACID AND (THIO) PHOSPHONIC ACID ESTERS AND AMIDES The invention relates to novel (thio)phosphoric and (thio)phosphonic acid derivatives of the formula 5 amines of formula R H or R H, i.e. compounds in which R and R, represent O-alkyl, NH-alkyl, or N- dialkyl. R The substituents R to R may have the following 5 meanings: 6-fluoro, 6-chloro, 6-bromo, 7-chloro, 7- 6 R 2 10 bromo, 5,8-dichloro-, 5,6,8-trichloro, 6-methyl, 2- 3 I methyl, 3-methyl, 6methoxy, 6-methylmercapto, 6- R R tert. butoxy, 6-ethoxy, 6-chloro-2-methyl, 6-chloro-3- 7 it methyl, 6chloro-5,8-dimethyl, the numbers indicating 8 the position of the substituents at the thiochromane nu- I cleus. Preferred are those compounds which are unsubin which stituted in the benzene moiety. R is O-alkyl, NHalkyl, or Ndialkyl, The thiochromanone oximes of formula Ill used as R is alkyl, O-alkyl, or phenyl, the alkyl groups" of each starting material for carrying out the process of -the .in-

radical having one to 10 carbon atoms, vention as well as the salts"of"'th'es e""compounds are R,, and R are each hydrogen or lower alkyl, partly described in literature (for example J. Ind. R ,R,;,R ,R,, each are hydrogen, lower alkyl, halogen, Chem. Soc. 43, pages 521 et seq. (1966). Those not yet lower alkoxy, or lower alkylthio, disclosed may be prepared in an analogous manner. and X is oxygen or sulfur. The starting compounds of formula II are known and Preferred alkyl groups are those having one to four readily accessible on an industrial scale by convencarbon atoms, preferably methyl and ethyl. Preferred i n l m hods. h lo e re fl orine, chlorine o b i F The reaction is generally carried out with approxiamong h compounds f f l 1 th are preferred mately stoichiometric amounts of the reactants; a slight in which at least one of the radicals R and R and at excess (up to 10%) of compound Il may be of advanleast three of the radicals R to R are hydrogen. tage.

The present invention also relates to a process for the The reaction is preferably carried out in a solvent manufacture of compounds of formula which comthat is inert under the reaction conditions, for example prises reacting (thio)ph sphoric or (thio)phosphonic CthCI'S, SUCh as thl, diiSOpI'Opyl ether, glycol id ester or id id h lid f f l dimethyl ether, tetrahydrofurane, dioxane; ketones and nitriles, such as acetone, methylethyl ketone, methylisopropyl ketone, methylbutyl ketone, benzonitrile, H propionitrile, acetonitrile; benzene and alkyl benzenes, H such as toluene or xylene; halobenzenes, for example chlorobenzene, dichlorobenzene; as well as halogenated aliphatic compounds such as methylene chloride, With thiochromanone oximes 0f the formula 40 chloroform, carbon tetrachloride and dichloroethane. When free thiochromanone oximes of formula III are NOH used as starting materials a basic agent must be added 5 to bind the hydrogen halide set free. 6 Suitable acid-binding agents are especially alkali I11 metal alcoholates such as sodium or otassium meth l- R R y 14 ate or ethylate; sodium hydride, alkali metal carbonates R such as sodium carbonate and potassium carbonate, as

well as tertiary bases, for example triethyl amine or pyridine.

either per se in the presence of acid-binding agents, or in the form of their salts, ha] in formula ll preferably being chlorine or bromine. The reaction can be illustrated by the following scheme:

phosphonic acid ester or amide dihalides, i.e. compounds of formula II in which R or R also represents ha]. The ester halides or amide halides of formula 1 (R or R hal) obtained are then reacted with alcohols or Instead of the free thiochromanone oximes there may also be used the salts thereof, preferably the alkali metal and alkaline earth metal salts. In this case a basic agent need not be added.

According to a modification of the process of the invention the thiochromanone oximes of formula [II can also be reacted with (thiono)phosphoric or (thiono)- The process of the invention can be carried out within a wide temperature range. In general, it is performed at room temperature or slightly or moderately elevated temperature, preferably in the range of from 20 to 100C. In most cases the reaction is exothermic and, therefore, it is often necessary, especially at the beginning of the reaction, to cool the reaction mixture Suitable dispersing agents are cellulose pitch (salts of lignin-sulfonic acids), salts of naphthalenesulfonic acid or, in certain cases, hydrated silicic acids or kieselguhr.

As grinding auxiliaries, suitable inorganc or organic from the outside. To complete the reaction it has 5 salts, for example sodium sulfate, ammonium sulfate, proved advantageous to continue stirring for a prosodium carbonate and sodium bicarbonate, sodium longed period of time (one to three hours) while heatthiosulfate, sodium stearate, or sodium acetate may be ing. used.

After distillation of the solvent the reaction products Simple compositions suitable for testing the activity are obtained in the form of oils which crystallize in of the compounds may be obtained in the following some cases. manner:

The compounds of formula I are novel and represent WETTABLE POWDER a new class of phosphoric and phosphomc acld esters.

While having a very low toxicity to warm-blooded anig of f f are ground 6 of finely mals they possess a good pesticidal especially insectil5 dlperse d slhclc and Subseflufmfly mlxed "f cidal, acaricidal and nematocidal activity. In the field mlxer 48 g 9 mlxture Contammg 133% otidljled of plant protection they are particularly useful for comcellulose Waste q i 653% of Q i t? andfllumlmum bating noxious sucking and biting insects and mites. Silicate; 153% of finely dispersed. 5111910 i 47% of Another advantage of the compounds is the fact that p yp py y and 13% of the sodlum Salt of they are active against parasite stains which are resis- Oleylmethylt'fwnde" Thus 60 g ofa 10% wettable tant to other pesticides. der are Obtained The phosphoric and phosphonic acid derivatives of EMULSIFIABLE CONCENTRATE the invention may be formulated in admixture with solid or liquid inert carrier substances, adhesives, wet- 2 2 gf l kaftlve suinst'imcel, I: g of cyciohexanon; ans ting and dispersing agents, or grinding auxiliaries in the g 0 a y ary yg yco ct er f CO 0 are mlxe each other. 20 g of a 10% emulslfiable concentrate are form of wettable powders, emulsions, suspensions,

obtalned. dustlng powders, granules, fly-bands, and products for The f H i E l S mu tr t thei v n spreading and washing. They may be mixed with other 0 ow ng Xamp e s a e n en lo insecticides, fungicides, nematocides and herbicides. GENERAL INSTRUCTION s f matenal f f i f i 0.1 M01 of an oxime of formula 111 is dissolved in 150 ll ii i' t 81 S i ml of glycol dimethyl ether and the solution is added ii z $1 i? 6 s dropwise while stirring to a suspension of 0.1 mol of so- F S can ar dium hydride in 30 ml of glycol dimethyl ether. When P p 0 t z f f gF w] Spec: the addition is completed the mixture is stirred for andddlFweS or xamp C W stearate" 5 other 30 minutes. If necessary, the temperature is kept carrler material for llquld preparations all usual and below +3ooc by external cooling Next a solution of sultable Organic solvffms may be emplPyed, for exam- 0.11 mol of an acid chloride of formula 11 is added toluene, lene, dlacetone alcohol, lsophorot g dropwise at a rate such that the internal temperature of Olmes l dloxan, dlmethyl formamlde the mixture does not exceed +30C. Stirring is continmethyl sulfoxlde, ethyl acetate, butyl acetate, tetrahyued f 3 hours at room temperature The mixture is drofurane and ChlOrObenZeHethen diluted with 0.5 l of benzene, the organic phase is Suitable adhesives are glue-like cellulose products or Separated, h hl h d i h water, d d i d polyvinyl alcohols. over sodium sulfate. After distillation of the solvent the AS W tting g all Suitable emulsifiers y be reaction products are obtained in the form of oils which used. For example ethoxylated alkylphenols, salts of partly crystallize o b i unrated, arylor alkyl-aryl-sulfonic acids, salts of ethoxylated The com ounds listed in the following table were benzenesulfonic acids, or soaps. prepared by this method.

n or melting yield mol. Analysis Example structural formula point (m.p.) sum formula weight calc. found s 43.6 C 43.3 II 4.6 H 4.5 1 N-OP(OCH n,, 1.6113 71 C H NO PS 303 4.6 N 4.6 11 10.2 P 10.4 @K I 21.1 s 21.4

S 47.] C 45.6 II 5.4 H 5.8 2 N-0-P 0C,H,,) 11,, 1.5479 82 C, ,H,,.N0,,1 s 331 4.2 N 4.3 9.4 P 9.7 g :I 19.3 s 19.3

11 011 47.8 c 43.7 NO-P "54:11; 5.7 0C H, m. 62-63C 65 C H NO PS 301 10.2 P 9.7 21.3 s 21.1

('onlinued n,, or melting yield moi. Analysis Example structural fonnula point (m.p.) sum formula weight calc. found S ll CH 49.5 C 48.9 NOP 5.7 H 5.9 44 CH OC H n 1,5959 94 C H NO PS 315 4.4 N 4.2 l 3 9.8 P 9.7 w 20.3 s 20.3

S H CH 49.7 C 49.0 NOP 6.0 H 6.1 45 N(CH;,) n 1,6158 78 C H N OPS 314 8.9 N 8.7 1 3 9.9 P 9.6 20.4 S 20.1

ll CH NOP 52.4 C 52.3 46 g N(CH m.p. 88-89C 35 C, H N O PS 298 6.4 H 6.2 3 10.7 s 11.1

S H NOP(OC l-l 47 CH 3 5 ll m.p. 7l-72C 49 C ,,H NO PS 377 8.3 P 8.9 @i D 25.4 s 25.1

S H CH NO 4.8 H 4.8 48 11 mcrm m.p. 100-112C c n ctlr ors 334.5 8.4 N 8.4 @i D 9.3 9.4

s l Cl II CH NOP 45.2 C 45.6 49 N(CH m.p.89-100C 47 c i-l cm o ps 318.5 5.0 H 5.1 @i 1 8.4 N 8.4

EXAMPLE 50 Commercial phosphoric acid esters used for compar- Horse beans (Vicia faba) strongly infested with bean aphids (Doralisfabae) were sprayed to the drip-off with the aqueous dilution of an emulsion concentrate con- 50 taining as active ingredient 0.003% by weight of the compound of Example 1. The sprayed plants were placed in the greenhouse at 20C and the result was evaluated 24 hours after spraying. It was found that all aphids had been killed.

Compounds of Examples 2, 5, 6, 23, and 42 tested in the same manner showed an equally good effect.

EXAMPLE 51 Apple trees in pots strongly infested with a strain of 0 PE resistant fruit tree red spiders (Metatetranychus ulmi) were sprayed to the drip-off with the aqueous dilution of an emulsion concentrate containing as active ingredient 0.025% by weight of the compound of Example 3 and the plants were placed in the greenhouse at 20C. Examination under a microscope 8 days after the treatment showed that all movable stages of the mites had been killed.

Compounds of Examples 6, 7, 14 and 18 tested in the same manner showed an equally good effect.

ison did not exhibit any effect when applied in the same or even in higher concentration:

phenkapton 0.025 by weight without effect methyl demeton 0.05 by weight without effect dimethoate 0.05 by weight without effect EXAMPLE 52 EXAMPLE 53 The bottoms and insides of five Petri dishes having a diameter of 9 cm were uniformly sprayed with 1 cc each of a 0.003% acetonic solution of the compound of Example 3. After evaporation of the acetone 10 German cockroaches (Phyllodromia germanica) were placed in each dish. Within 2 hours all animals were in the permanent dorsal position (moribund state) and died.

The compound of Example 6 used in the same concentration had an equally good effect.

EXAMPLE 54 The bottoms and insides of five Petri dishes having a diameter of 9 cm were uniformly sprayed with 1 cc each of a 0.003% acetonic solution of the compound of Example 25. After evaporation of the acetone 10 house flies (musca domestica) were placed in each dish. Within 30 minutes all flies were in permanent dorsal position (moribund state) and died.

Under identical conditions the compound of Example 43 had an equally good effect.

We claim:

1. Compound of the formula 3. The compound of the formula 4. The compound of the formula S. The compound of the formula in which R, is O-alkyl, NH-alkyl, or Ndialkyl, R is alkyl, O-alkyl, or phenyl, R and R are each hydrogen or lower alkyl, R R R R are each hydrogen, halogen, lower alkyl, lower alkoxy or lower alkylthio, the alkyl constituent of each of R, to R having 1 to 4 carbon atoms, and X is oxygen or sulfur.

7. The compound of claim 6 wherein said halogen is fluorine, chlorine or bromine, the alkyl constituent of each of R to R is methyl or ethyl and at least one of R and R and at least three of R to R are hydrogen.

8. The compound of claim 6 wherein the substituents R to R are selected from the group consisting of 6- fluoro, 6-chloro, 6-bromo, 7-chloro, 7-brom0, 5,8- dichloro-, 5,6,8-trichl0ro, 6-methyl, 2-methyl, 3- methyl, 6-methoxy, 6-methylmercapto, 6-tert. butoxy, 6-ethoxy, 6-chloro-2-methyl, 6-chloro-3-methyl, 6- chloro-5,8dimethyl, said numbers indicating the position of the substituents at the thiochromane nucleus.

9. The compound of claim 6 wherein X is oxygen.

10. The compound of claim 6 wherein X is sulfur.

11. The compound of claim 6 wherein R, is methyl, R is ethoxy, R to R are each hydrogen and X is sulfur.

12. The compound of claim 6 wherein R, and R are each methoxy, R is fluorine, R R R R and R, are each hydrogen and X is sulfur.

13. The compound of claim 6 wherein R, and R are each ethoxy, R is fluorine, R R R R and R are each hydrogen and X is sulfur.

14. The compound of claim 6 wherein R, is methyl, R is ethoxy, R is fluorine, R R R R and R are each hydrogen and X is sulfur.

15. The compound of claim 6 wherein R, and R are each ethoxy, R is chlorine and R R R R and R are each hydrogen and X is sulfur.

16. The compound of claim 6 wherein R, and R are each ethoxy, R is bromine, R R R R and R are each hydrogen and X is sulfur. 

1. COMPOUND OF THE FORMULA
 2. The compound of the formula
 3. The compound of the formula
 4. The compound of the formula
 5. The compound of the formula
 6. Compound of the formula
 7. The compound of claim 6 wherein said halogen is fluorine, chlorine or bromine, the alkyl constituent of each of R3 to R8 is methyl or ethyl and at least one of R3 and R4 and at least three of R5 to R8 are hydrogen.
 8. The compound of claim 6 wherein the substituents R3 to R8 are selected from the group consisting of 6-fluoro, 6-chloro, 6-bromo, 7-chloro, 7-bromo, 5,8-dichloro-, 5,6,8-trichloro, 6-methyl, 2-methyl, 3-methyl, 6-methoxy, 6-methylmercapto, 6-tert. butoxy, 6-ethoxy, 6-chloro-2-methyl, 6-chloro-3-methyl, 6-chloro-5,8-dimethyl, said numbers indicating the position of the substituents at the thiochromane nucleus.
 9. The compound of claim 6 wherein X is oxygen.
 10. The compound of claim 6 wherein X is sulfur.
 11. The compound of claim 6 wherein R1 is methyl, R2 is ethoxy, R3 to R8 are each hydrogen and X is sulfur.
 12. The compound of claim 6 wherein R1 and R2 are each methoxy, R6 is fluorine, R3, R4, R5, R7 and R8 are each hydrogen and X is sulfur.
 13. The compound of claim 6 wherein R1 and R2 are each ethoxy, R6 is fluorine, R3, R4, R5, R7 and R8 are each hydrogen and X is sulfur.
 14. The compound of claim 6 wherein R1 is methyl, R2 is ethoxy, R6 is fluorine, R3, R4, R5, R7 and R8 are each hydrogen and X is sulfur.
 15. The compound of claim 6 wherein R1 and R2 are each ethoxy, R6 is chlorine and R3, R4, R5, R7 and R8 are each hydrogen and X is sulfur.
 16. The compound of claim 6 wherein R1 and R2 are each ethoxy, R6 is bromine, R3, R4, R5, R7 and R8 are each hydrogen and X is sulfur. 